U.S. patent application number 12/677445 was filed with the patent office on 2011-01-06 for fullerene derivative.
This patent application is currently assigned to SUMITOMO CHEMICAL COMPANY LIMITED. Invention is credited to Toshiyuki Itoh, Yasunori Uetani.
Application Number | 20110001093 12/677445 |
Document ID | / |
Family ID | 40658144 |
Filed Date | 2011-01-06 |
United States Patent
Application |
20110001093 |
Kind Code |
A1 |
Itoh; Toshiyuki ; et
al. |
January 6, 2011 |
FULLERENE DERIVATIVE
Abstract
Disclosed is an organic photoelectric converter having a layer
containing a fullerene derivative represented by the formula (1)
below. (In the formula (1), m represents an integer of 1-6; n
represents an integer of 1-4; p represents an integer of 0-5; r
represents an integer of 0-4; and Q represents a group represented
by the formula (2) or (3) below. When there are a plurality of m's,
they may be the same as or different from each other. In the
formulae (2) and (3), R.sup.1 and R.sup.2 independently represent a
halogen atom, an alkyl group, an alkoxy group or an aryl group, and
a hydrogen atom contained in these groups may be substituted by a
halogen atom; q represents an integer of 0-7; and v represents an
integer of 0-5. When there are a plurality of R.sup.1's, they may
be the same as or different from each other. When there are a
plurality of R.sup.2's, they may be the same as or different from
each other.) ##STR00001##
Inventors: |
Itoh; Toshiyuki;
(Tottori-shi, JP) ; Uetani; Yasunori;
(Tsukuba-shi, JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 PENNSYLVANIA AVENUE, N.W., SUITE 800
WASHINGTON
DC
20037
US
|
Assignee: |
SUMITOMO CHEMICAL COMPANY
LIMITED
Chuo-ku ,Tokyo
JP
NATIONAL UNIVERSITY CORPORATION TOTTORI UNIVERSITY
Tottori-shi ,Tottori
JP
|
Family ID: |
40658144 |
Appl. No.: |
12/677445 |
Filed: |
September 11, 2008 |
PCT Filed: |
September 11, 2008 |
PCT NO: |
PCT/JP2008/066395 |
371 Date: |
March 10, 2010 |
Current U.S.
Class: |
252/500 ;
548/417; 977/738; 977/948 |
Current CPC
Class: |
H01L 51/0036 20130101;
C07D 209/96 20130101; C08K 5/3417 20130101; H01L 51/0047 20130101;
H01L 51/4253 20130101; Y02E 10/549 20130101; B82Y 10/00
20130101 |
Class at
Publication: |
252/500 ;
548/417; 977/738; 977/948 |
International
Class: |
H01B 1/12 20060101
H01B001/12; C07D 487/00 20060101 C07D487/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 12, 2007 |
JP |
2007-236372 |
May 15, 2008 |
JP |
2008-128098 |
Claims
1. An organic photoelectric conversion device comprising a layer
comprising a fullerene derivative represented by the following
formula (1): ##STR00034## wherein m represents an integer of 1 to
6, n represents an integer of 1 to 4, p represents an integer of 0
to 5, and r represents an integer of 0 to 4; Q represents a group
represented by the following formula (2) or (3); and when there is
a plurality of m, the m may be the same or different, ##STR00035##
wherein R.sup.1 and R.sup.2 each independently represent a halogen
atom, an alkyl group, an alkoxy group, or an aryl group; a hydrogen
atom included in these groups may be replaced by a halogen atom; q
represents an integer of 0 to 7, and v represents an integer of 0
to 5; when there is a plurality of R.sup.1, the R.sup.1 may be the
same or different; and when there is a plurality of R.sup.2, the
R.sup.2 may be the same or different.
2. A composition comprising a fullerene derivative represented by
the following formula (1) and an electron-donating compound,
##STR00036## wherein m represents an integer of 1 to 6, n
represents an integer of 1 to 4, p represents an integer of 0 to 5,
and r represents an integer of 0 to 4; Q represents a group
represented by the following formula (2) or (3); and when there is
a plurality of m, the m may be the same or different, ##STR00037##
wherein R.sup.1 and R.sup.2 each independently represent a halogen
atom, an alkyl group, an alkoxy group, or an aryl group; a hydrogen
atom included in these groups may be replaced by a halogen atom; q
represents an integer of 0 to 7, and v represents an integer of 0
to 5; when there is a plurality of R.sup.1, the R.sup.1 may be the
same or different; and when there is a plurality of R.sup.2, the
R.sup.2 may be the same or different.
3. The composition according to claim 2, wherein the
electron-donating compound is a polymer compound.
4. An organic photoelectric conversion device comprising a layer
comprising a composition according to claim 2.
5. A fullerene derivative represented by the following formula (4):
##STR00038## wherein c represents an integer of 1 to 6, d
represents an integer of 1 to 4, e represents an integer of 0 to 5,
and f represents an integer of 0 to 4; T represents a group
represented by the following formula (5) or (6); and when there is
a plurality of c, the c may be the same or different, ##STR00039##
wherein R.sup.3 and R.sup.4 each independently represent a halogen
atom, an alkyl group, an alkoxy group, or an aryl group; a hydrogen
atom included in these groups may be replaced by a halogen atom; g
represents an integer of 0 to 7, and h represents an integer of 0
to 5, provided that when h is 0, f is an integer of 1 to 4; when
there is a plurality of R.sup.3, the R.sup.3 may be the same or
different; and when there is a plurality of R.sup.4, the R.sup.4
may be the same or different.
6. An organic photoelectric conversion device comprising a layer
comprising a composition according to claim 3.
Description
TECHNICAL FIELD
[0001] The present invention relates to a fullerene derivative and
an organic photoelectric conversion device using the same.
BACKGROUND ART
[0002] Organic semiconductor materials having charge (electron and
hole) transport properties have been studied for application to
organic photoelectric conversion devices (organic solar cells,
optical sensors, and the like) and the like. For example, organic
solar cells using fullerene derivatives have been investigated. For
example, [6,6]-phenyl C61-butyric acid methyl ester (hereinafter
sometimes referred to as [60]-PCBM) has been known as a fullerene
derivative (see NON-PATENT DOCUMENT 1).
NON-PATENT DOCUMENT 1: Advanced Functional Materials, Vol. 13, p.
85 (2003)
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0003] However, a problem of an organic photoelectric conversion
device comprising [60]-PCBM is that the conversion efficiency is
not always sufficient.
[0004] Accordingly, it is an object of the present invention to
provide an organic photoelectric conversion device having high
conversion efficiency. It is another object of the present
invention to provide a fullerene derivative having excellent
solubility in organic solvents.
Means for Solving the Problems
[0005] First, the present invention provides an organic
photoelectric conversion device comprising a layer comprising a
fullerene derivative represented by the following formula (1):
##STR00002##
wherein m represents an integer of 1 to 6, n represents an integer
of 1 to 4, p represents an integer of 0 to 5, and r represents an
integer of 0 to 4; Q represents a group represented by the
following formula (2) or (3); and when there is a plurality of m,
the m may be the same or different,
##STR00003##
wherein R.sup.1 and R.sup.2 each independently represent a halogen
atom, an alkyl group, an alkoxy group, or an aryl group; a hydrogen
atom included in these groups may be replaced by a halogen atom; q
represents an integer of 0 to 7, and v represents an integer of 0
to 5; when there is a plurality of R.sup.1, the R.sup.1 may be the
same or different; and when there is a plurality of R.sup.2, the
R.sup.2 may be the same or different.
[0006] Secondly, the present invention provides a composition
comprising a fullerene derivative represented by the following
formula (1) and an electron-donating compound,
##STR00004##
wherein m represents an integer of 1 to 6, n represents an integer
of 1 to 4, p represents an integer of 0 to 5, and r represents an
integer of 0 to 4; Q represents a group represented by the
following formula (2) or (3); and when there is a plurality of m,
the m may be the same or different,
##STR00005##
wherein R.sup.1 and R.sup.2 each independently represent a halogen
atom, an alkyl group, an alkoxy group, or an aryl group; a hydrogen
atom included in these groups may be replaced by a halogen atom; q
represents an integer of 0 to 7, and v represents an integer of 0
to 5; when there is a plurality of R.sup.1, the R.sup.1 may be the
same or different; and when there is a plurality of R.sup.2, the
R.sup.2 may be the same or different.
[0007] Thirdly, the present invention provides an organic
photoelectric conversion device comprising a layer comprising the
composition.
[0008] Fourthly, the present invention provides a fullerene
derivative represented by the following formula (4):
##STR00006##
wherein c represents an integer of 1 to 6, d represents an integer
of 1 to 4, e represents an integer of 0 to 5, and f represents an
integer of 0 to 4; T represents a group represented by the
following formula (5) or (6); and when there is a plurality of c,
the c may be the same or different,
##STR00007##
wherein R.sup.3 and R.sup.4 each independently represent a halogen
atom, an alkyl group, an alkoxy group, or an aryl group; a hydrogen
atom included in these groups may be replaced by a halogen atom; g
represents an integer of 0 to 7, and h represents an integer of 0
to 5, provided that when h is 0, f is an integer of 1 to 4; when
there is a plurality of R.sup.3, the R.sup.3 may be the same or
different; and when there is a plurality of R.sup.4, the R.sup.4
may be the same or different.
ADVANTAGE OF THE INVENTION
[0009] The organic photoelectric conversion device of the present
invention has high conversion efficiency.
BEST MODE FOR CARRYING OUT THE INVENTION
[0010] The present invention will be described below in detail.
<Fullerene Derivative Used in Organic Photoelectric Conversion
Device>
[0011] The organic photoelectric conversion device of the present
invention comprises a layer comprising a fullerene derivative
represented by the above formula (1). The fullerene derivative is a
C.sub.60 fullerene derivative. In the above formula (1), Q
represents a group represented by the above formula (2) or (3).
[0012] When the fullerene derivative used in the organic
photoelectric conversion device of the present invention has a
group represented by the above formula (2), R.sup.1 in the above
formula (2) represents a halogen atom, an alkyl group, an alkoxy
group, or an aryl group. A hydrogen atom included in these groups
may be replaced by a halogen atom. When there is a plurality of
R.sup.1, the R.sup.1 may be the same or different.
[0013] The alkyl group represented by R.sup.1 in the above formula
(2) generally has 1 to 20 carbon atoms, may be linear or branched,
and may be a cycloalkyl group. Specific examples of the alkyl group
include a methyl group, an ethyl group, an n-propyl group, an
isopropyl group, an n-butyl group, an isobutyl group, a t-butyl
group, an s-butyl group, a 3-methylbutyl group, an n-pentyl group,
an n-hexyl group, a 2-ethylhexyl group, an n-heptyl group, an
n-octyl group, an n-nonyl group, an n-decyl group, and an n-lauryl
group. A hydrogen atom in the above alkyl group may be replaced by
a halogen atom, examples of which include a monohalomethyl group, a
dihalomethyl group, a trihalomethyl group, and a pentahaloethyl
group. Preferably, a hydrogen atom is replaced by a fluorine atom
among halogen atoms.
[0014] Examples of the alkyl group in which a hydrogen atom is
replaced by a fluorine atom include a trifluoromethyl group, a
pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl
group, and a perfluorooctyl group.
[0015] The alkoxy group represented by R.sup.1 in the above formula
(2) generally has 1 to 20 carbon atoms, may be linear or branched,
and may be a cycloalkyloxy group. Specific examples of the alkoxy
group include a methoxy group, an ethoxy group, an n-propyloxy
group, an isopropyloxy group, an n-butoxy group, an isobutoxy
group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group,
an n-hexyloxy group, a cyclohexyloxy group, an n-heptyloxy group,
an n-octyloxy group, a 2-ethylhexyloxy group, an n-nonyloxy group,
an n-decyloxy group, a 3,7-dimethyloctyloxy group, and an
n-lauryloxy group. A hydrogen atom in the above alkoxy group may be
replaced by a halogen atom. Preferably, a hydrogen atom is replaced
by a fluorine atom among halogen atoms. Examples of the alkoxy
group in which a hydrogen atom is replaced by a fluorine atom
include a trifluoromethoxy group, a pentafluoroethoxy group, a
perfluorobutoxy group, a perfluorohexyl group, and a perfluorooctyl
group.
[0016] The aryl group represented by R.sup.1 in the above formula
(2) generally has 6 to 60 carbon atoms and may have a substituent.
Examples of the substituent of the aryl group include a linear or
branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl
group having 1 to 20 carbon atoms, and an alkoxy group comprising
in its structure a linear or branched alkyl group having 1 to 20
carbon atoms, or a cycloalkyl group having 1 to 20 carbon atoms.
Specific examples of the aryl group include a phenyl group, a
C.sub.1 to C.sub.12 alkoxyphenyl group (C.sub.1 to C.sub.12
indicates having 1 to 12 carbon atoms. The same applies
hereinafter.), a C.sub.1 to C.sub.12 alkylphenyl group, a
1-naphthyl group, and a 2-naphthyl group. An aryl group having 6 to
20 carbon atoms is preferred, and a C.sub.1 to C.sub.12
alkoxyphenyl group, and a C.sub.1 to C.sub.12 alkylphenyl group are
more preferred. A hydrogen atom in the above aryl group may be
replaced by a halogen atom. Preferably, a hydrogen atom is replaced
by a fluorine atom among halogen atoms.
[0017] Examples of the halogen atom represented by R.sup.1 in the
above formula (2) include a fluorine atom, a chlorine atom, a
bromine atom, and an iodine atom. In terms of conversion
efficiency, a fluorine atom is preferred.
[0018] In the above formula (1), m represents an integer of 1 to 6.
When there is a plurality of m, the m may be the same or different.
In terms of the ease of availability of the raw materials, m is
preferably 2. p represents an integer of 0 to 5. In terms of charge
transport properties, p is preferably an integer of 0 to 3. n
represents an integer of 1 to 4, and r represents an integer of 0
to 4.
[0019] In the above formula (2), q represents an integer of 0 to
7.
[0020] Specific examples of the fullerene derivative having a group
represented by the above formula (2) include the following
compounds.
##STR00008## ##STR00009## ##STR00010##
[0021] Among the fullerene derivatives having a group represented
by the above formula (2), fullerene derivatives represented by the
following formula (7) are preferred in terms of conversion
efficiency.
##STR00011##
wHerein R.sup.1, m, n, p, and q represent the same meanings as
described above.
[0022] In the above formula (7), m is preferably 2, n is preferably
2, p is preferably 0, and q is preferably 0 or 1, in terms of
conversion efficiency. R.sup.1 is preferably a fluorine atom or an
alkyl group having 1 to 4 carbon atoms. The alkyl group may be
substituted with a fluorine atom.
[0023] When the fullerene derivative used in the organic
photoelectric conversion device of the present invention has a
group represented by the above formula (3), R.sup.2 in the above
formula (3) represents a halogen atom, an alkyl group, an alkoxy
group, or an aryl group. A hydrogen atom included in these groups
may be replaced by a fluorine atom. When there is a plurality of
R.sup.2, the R.sup.2 may be the same or different.
[0024] The alkyl group represented by R.sup.2 in the above formula
(3) generally has 1 to 20 carbon atoms and includes the same groups
as the alkyl groups described for the above-described R.sup.1.
[0025] The alkoxy group represented by R.sup.2 in the above formula
(3) generally has 1 to 20 carbon atoms and includes the same groups
as the alkoxy groups described for the above-described R.sup.1.
[0026] The aryl group represented by R.sup.2 in the above formula
(3) generally has 6 to 60 carbon atoms and may have a substituent.
Examples of the aryl group include the same groups as the aryl
groups described for the above-described R.sup.1.
[0027] Examples of the halogen atom represented by R.sup.2 in the
above formula (3) include a fluorine atom, a chlorine atom, a
bromine atom, and an iodine atom. In terms of conversion
efficiency, a fluorine atom is preferred.
[0028] In the above formula (3), v represents an integer of 0 to 5.
In terms of conversion efficiency, v is preferably 0 or 1.
[0029] In terms of conversion efficiency, R.sup.2 is preferably an
alkyl group or a halogen atom, and more preferably a methyl group
or a fluorine atom.
[0030] Specific examples of the fullerene derivative having a group
represented by the above formula (3) include the following
compounds.
##STR00012## ##STR00013## ##STR00014##
[0031] Among the fullerene derivatives having a group represented
by the above formula (3), fullerene derivatives represented by the
following formula (8) are preferred in terms of conversion
efficiency.
##STR00015##
wherein R.sup.2, m, n, p, and v represent the same meanings as
described above.
[0032] In the above formula (8), m is preferably 2, n is preferably
2, p is preferably 0, and v is preferably 0 or 1, in terms of
conversion efficiency. R.sup.2 is preferably a halogen atom or an
alkyl group.
[0033] Among the fullerene derivatives represented by the above
formula (8), fullerene derivatives represented by the following
formula (9) are preferred in terms of conversion efficiency.
##STR00016##
wherein m, n, and p represent the same meanings as described above;
and R.sup.5 represents a fluorine atom or an alkyl group having 1
to 4 carbon atoms.
[0034] In the above formula (9), m is preferably 2, n is preferably
2, and p is preferably 0, in terms of conversion efficiency.
R.sup.5 is preferably a fluorine atom or a methyl group.
[0035] For a method for synthesizing the fullerene derivative
represented by the above formula (1), for example, the fullerene
derivative can be synthesized by the 1,3-dipolar cycloaddition
reaction of O.sub.60 fullerene and iminium cations produced by the
decarboxylation of imine produced from a glycine derivative and
aldehyde (Prato reaction, Accounts of Chemical Research, Vol. 31,
519-526 (1998)).
[0036] Examples of the glycine derivative used here include
N-methoxymethylglycine and N-(2-(2-methoxyethoxy)ethyl)glycine. The
amount of these glycine derivatives used is generally in the range
of 0.1 to 10 moles, preferably 0.5 to 3 moles, with respect to 1
mole of fullerene.
[0037] Examples of aldehyde, the other raw material of the
substituent, include benzaldehyde and naphthoaldehyde. The amount
of these aldehydes used is generally in the range of 0.1 to 10
moles, preferably 0.5 to 4 moles, with respect to 1 mole of
fullerene.
[0038] Generally, this reaction is performed in a solvent. In this
case, as the solvent, a solvent inert to this reaction, for
example, toluene, xylene, hexane, octane, or chlorobenzene, is
used. The amount of the solvent used is generally in the range of 1
to 100000 times by weight the amount of fullerene.
[0039] In reaction, for example, a glycine derivative, aldehyde,
and fullerene should be mixed in a solvent and reacted by heating.
The reaction temperature is generally in the range of 50 to
350.degree. C. The reaction time is generally 30 minutes to 50
hours.
[0040] After the heating reaction, the reaction mixture is allowed
to cool to room temperature, and the solvent is evaporated under
reduced pressure by a rotary evaporator. The obtained solids are
separated and purified by silica gel flash column chromatography,
thereby, the target fullerene derivative can be obtained.
[0041] <Organic Photoelectric Conversion Device>
[0042] The organic photoelectric conversion device of the present
invention comprises a pair of electrodes, at least one of which is
transparent or semitransparent, and a layer comprising the
fullerene derivative used in the present invention, between the
electrodes. The fullerene derivative used in the present invention
can be used as an electron-accepting compound and as an
electron-donating compound, but is preferably used as an
electron-accepting compound.
[0043] Next, the operation mechanism of the organic photoelectric
conversion device will be described. Light energy entering from the
transparent or semitransparent electrode is absorbed by the
electron-accepting compound and/or the electron-donating compound
to produce excitons in which an electron and a hole are bound. When
the produced excitons move and reach the heterojunction interface
where the electron-accepting compound and the electron-donating
compound are adjacent to each other, electrons and holes separate,
due to their difference in HOMO energy and LUMO energy at the
interface, to generate charges (electrons and holes) that can move
independently. The generated charges move to the electrodes
respectively, thereby, the charges can be extracted as electric
energy (current) to the outside.
[0044] As specific examples of the organic photoelectric conversion
device of the present invention, either of the following is
preferred:
1. an organic photoelectric conversion device comprising a pair of
electrodes, at least one of which is transparent or
semitransparent, a first layer provided between the electrodes and
containing the fullerene derivative used in the present invention,
as an electron-accepting compound, and a second layer containing an
electron-donating compound, provided adjacent to the first layer;
and 2. an organic photoelectric conversion device comprising a pair
of electrodes, at least one of which is transparent or
semitransparent, and at least one layer provided between the
electrodes and containing the fullerene derivative used in the
present invention, as an electron-accepting compound, and an
electron-donating compound.
[0045] In terms of comprising many heterojunction interfaces, the
organic photoelectric conversion device of the above 2. is
preferred. Also, in the organic photoelectric conversion device of
the present invention, an additional layer may be provided between
at least one electrode and the layer comprising the fullerene
derivative used in the present invention. Examples of the
additional layer include a charge transport layer for transporting
holes or electrons.
[0046] In the organic photoelectric conversion device of the above
2, the proportion of the fullerene derivative in the organic layer
containing the fullerene derivative and the electron-donating
compound is preferably 10 to 1000 parts by weight, more preferably
50 to 500 parts by weight, based on 100 parts by weight of the
electron-donating compound.
[0047] The layer comprising the fullerene derivative used in the
organic photoelectric conversion device of the present invention is
preferably formed of an organic thin film comprising the fullerene
derivative. The thickness of the organic thin film is generally 1
nm to 100 .mu.m, preferably 2 nm to 1000 nm, more preferably 5 nm
to 500 nm, and further preferably 20 nm to 200 nm.
[0048] The above electron-donating compound is preferably a polymer
compound, in terms of coating properties. Examples thereof include
polyvinylcarbazole and its derivatives, polysilane and its
derivatives, polysiloxane derivatives having aromatic amine in the
side chain or the main chain, polyaniline and its derivatives,
polythiophene and its derivatives, polypyrrole and its derivatives,
polyphenylenevinylene and its derivatives, polythienylenevinylene
and its derivatives, and polyfluorene and its derivatives.
[0049] The present invention also relates to a composition
comprising the above fullerene derivative and the above
electron-donating compound, which is used for forming the organic
electrons of the organic photoelectric conversion device of the
present invention.
[0050] In terms of conversion efficiency, the electron-donating
compound used in the organic photoelectric conversion device is
preferably a polymer compound having a repeating unit selected from
the group consisting of the following formula (10) and the
following formula (11), more preferably a polymer compound having a
repeating unit represented by the following formula (10):
##STR00017##
wherein R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11,
R.sup.12, R.sup.13, R.sup.14, and R.sup.15 each independently
represent a hydrogen atom, an alkyl group, an alkoxy group, or an
aryl group.
[0051] When R.sup.5 and R.sup.7 in the above formula (10) are alkyl
groups, specific examples of the alkyl groups include the same
alkyl groups as illustrated for the above-described R'. When
R.sup.6 and R.sup.7 are alkoxy groups, specific examples of the
alkoxy groups include the same alkoxy groups as illustrated for the
above-described R.sup.1. When R.sup.6 and R.sup.7 are aryl groups,
specific examples of the aryl groups include the same aryl groups
as illustrated for the above-described R.sup.1.
[0052] In the above formula (10), at least one of R.sup.6 and
R.sup.7 is preferably an alkyl group having 1 to 20 carbon atoms,
more preferably an alkyl group having 4 to 8 carbon atoms, in terms
of conversion efficiency.
[0053] When R.sup.8 to R.sup.15 in the above formula (11) are alkyl
groups, specific examples of the alkyl groups include the same
alkyl groups as illustrated for the above-described R.sup.1. When
R.sup.8 to R.sup.15 are alkoxy groups, specific examples of the
alkoxy groups include the same alkoxy groups as illustrated for the
above-described R.sup.1. When R.sup.8 to R.sup.15 are aryl groups,
specific examples of the aryl groups include the same aryl groups
as illustrated for the above-described R.sup.1.
[0054] In the above formula (11), R.sup.10 to R.sup.15 are
preferably hydrogen atoms, in terms of the ease of synthesis of the
monomer. Also, in terms of conversion efficiency, R.sup.8 and
R.sup.9 are preferably an alkyl group having 1 to 20 carbon atoms,
or an aryl group having 6 to 20 carbon atoms, more preferably an
alkyl group having 5 to 8 carbon atoms, or an aryl group having 6
to 15 carbon atoms.
[0055] The organic photoelectric conversion device of the present
invention is generally formed on a substrate. This substrate should
be one that does not change when electrodes are formed, and a layer
of an organic substance is formed. Examples of the material of the
substrate include glass, plastic, a polymer film, and silicon. In
the case of an opaque substrate, the opposite electrode (that is,
the electrode far from the substrate) is preferably transparent or
semitransparent.
[0056] Examples of the above transparent or semitransparent
electrode material include a conductive metal oxide film and a
semitransparent metal thin film. Specifically, films fabricated
using conductive materials of indium oxide, zinc oxide, tin oxide,
and composites thereof, indium tin oxide (ITO) and indium zinc
oxide, and the like (NESA and the like), as well as gold, platinum,
silver, copper, and the like are used. ITO, indium zinc oxide, and
tin oxide are preferred. Examples of the method for fabricating the
electrode include vacuum deposition, sputtering, ion plating, and
plating. Also, organic transparent conductive films of polyaniline
and its derivatives, polythiophene and its derivatives, and the
like may be used as the electrode material. Further, metal, a
conductive polymer, and the like can be used as the electrode
material, and preferably, one electrode of the pair of electrodes
is preferably a material having a small work function. For example,
metal, such as lithium, sodium, potassium, rubidium, cesium,
magnesium, calcium, strontium, barium, aluminum, scandium,
vanadium, zinc, yttrium, indium, cerium, samarium, europium,
terbium, and ytterbium, and alloys of two or more thereof, or
alloys of one or more thereof and one or more of gold, silver,
platinum, copper, manganese, titanium, cobalt, nickel, tungsten,
and tin, graphite or graphite intercalation compounds, and the like
are used.
[0057] Examples of the alloys include a magnesium-silver alloy, a
magnesium-indium alloy, a magnesium-aluminum alloy, an
indium-silver alloy, a lithium-aluminum alloy, a lithium-magnesium
alloy, a lithium-indium alloy, and a calcium-aluminum alloy.
[0058] As the material used as a buffer layer as an additional
layer, alkali metal, such as lithium fluoride, alkaline earth metal
halide and oxide, and the like can be used. Also, fine particles of
an inorganic semiconductor, such as titanium oxide, can be
used.
<Method for Manufacturing Organic Thin Film>
[0059] The method for manufacturing the above organic thin film is
not particularly limited, and includes, for example, a method of
film formation from a solution comprising the fullerene derivative
used in the present invention.
[0060] The solvent used for film formation from a solution is not
particularly limited as long as the fullerene derivative used in
the present invention is dissolved. Examples of this solvent
include hydrocarbon solvents, such as toluene, xylene, mesitylene,
tetralin, decalin, bicyclohexyl, n-butylbenzene, s-butylbenzene,
and t-butylbenzene, halogenated saturated hydrocarbon solvents,
such as carbon tetrachloride, chloroform, dichloromethane,
dichloroethane, chlorobutane, bromobutane, chloropentane,
bromopentane, chlorohexane, bromohexane, chlorocyclohexane, and
bromocyclohexane, halogenated unsaturated hydrocarbon solvents,
such as chlorobenzene, dichlorobenzene, and trichlorobenzene, and
ether solvents, such as tetrahydrofuran and tetrahydropyran.
Generally, 0.1 wt % or more of the above fullerene derivative can
be dissolved in the above solvent.
[0061] The above solution may further comprise a polymer compound.
Specific examples of the solvent used in the solution include the
above-described solvents, but in terms of the solubility of the
polymer compound, aromatic hydrocarbon solvents are preferred, and
toluene, xylene, and mesitylene are more preferred.
[0062] For film formation from a solution, coating methods, such as
spin coating, casting, microgravure coating, gravure coating, bar
coating, roll coating, wire bar coating, dip coating, spray
coating, screen printing, flexographic printing, offset printing,
ink jet printing, dispenser printing, nozzle coating, and capillary
coating, can be used, and spin coating, flexographic printing, ink
jet printing, and dispenser printing are preferred.
[0063] In the organic photoelectric conversion device, by allowing
light, such as sunlight, to enter from the transparent or
semitransparent electrode, photoelectromotive force is generated
between the electrodes, thereby, the organic photoelectric
conversion device can be operated as an organic thin film solar
cell. By integrating a plurality of organic thin film solar cells,
they can also be used as an organic thin film solar cell
module.
[0064] Also, by allowing light to enter from the transparent or
semitransparent electrode, with voltage applied between the
electrodes, light current flows, thereby, the organic photoelectric
conversion device can be operated as an organic optical sensor. By
integrating a plurality of organic optical sensors, they can also
be used as an organic image sensor.
<Fullerene Derivative>
[0065] The fullerene derivative of the present invention is
represented by the above formula (4). In the above formula (4), T
is a group represented by the above formula (5) or (6). The
fullerene derivative has excellent solubility in organic solvents,
particularly, aromatic hydrocarbon solvents, such as toluene,
xylene, and mesitylene.
[0066] When the fullerene derivative of the present invention has a
group represented by the above formula (5), R.sup.3 in the above
formula (5) represents a halogen atom, an alkyl group, an alkoxy
group, or an aryl group. A hydrogen atom included in these groups
may be replaced by a halogen atom. When there is a plurality of
R.sup.3, the R.sup.3 may be the same or different.
[0067] The alkyl group represented by R.sup.3 in the above formula
(5) generally has 1 to 20 carbon atoms and includes the same groups
as the alkyl groups described for the above-described R.sup.1.
[0068] The alkoxy group represented by R.sup.3 in the above formula
(5) generally has 1 to 20 carbon atoms and includes the same groups
as the alkoxy groups described for the above-described R.sup.1.
[0069] The aryl group represented by R.sup.3 in the above formula
(5) generally has 6 to 60 carbon atoms and may have a substituent.
Examples of the aryl group include the same groups as the aryl
groups described for the above-described R.sup.1.
[0070] Examples of the halogen atom represented by R.sup.3 in the
above formula (5) include a fluorine atom, a chlorine atom, a
bromine atom, and an iodine atom. In terms of conversion efficiency
when the fullerene derivative is used in the organic photoelectric
conversion device, a fluorine atom is preferred.
[0071] In the above formula (4), c represents an integer of 1 to 6.
When there is a plurality of c, the c may be the same or different.
In terms of the ease of availability of the raw materials, 2 is
preferred. d represents an integer of 0 to 5. In terms of charge
transport properties, 0 to 3 are preferred. e represents an integer
of 1 to 4, and f represents an integer of 0 to 4.
[0072] In the above formula (5), g represents an integer of 0 to
7.
[0073] Among the fullerene derivatives having a group represented
by the above formula (5), fullerene derivatives represented by the
following formula (12) are preferred in terms of conversion
efficiency when the fullerene derivative is used in the organic
photoelectric conversion device.
##STR00018##
wherein R.sup.3, c, d, e, and g represent the same meanings as
described above.
[0074] In the above formula (12), c is preferably 2, d is
preferably 2, e is preferably 0, and g is preferably 0 or 1, in
terms of conversion efficiency when the fullerene derivative is
used in the organic photoelectric conversion device. R.sup.3 is
preferably a fluorine atom or an alkyl group having 1 to 4 carbon
atoms. The alkyl group may be substituted with a fluorine atom.
[0075] When the fullerene derivative of the present invention has a
group represented by the above formula (6), R.sup.4 in the above
formula (6) represents a halogen atom, an alkyl group, an alkoxy
group, or an aryl group. A hydrogen atom included in these groups
may be replaced by a fluorine atom. When there is a plurality of
R.sup.4, the R.sup.4 may be the same or different.
[0076] The alkyl group represented by R.sup.4 in the above formula
(6) generally has 1 to 20 carbon atoms and includes the same groups
as the alkyl groups described for the above-described R.sup.1.
[0077] The alkoxy group represented by R.sup.4 in the above formula
(6) generally has 1 to 20 carbon atoms and includes the same groups
as the alkoxy groups described for the above-described R.sup.1.
[0078] The aryl group represented by R.sup.4 in the above formula
(6) generally has 6 to 60 carbon atoms and may have a substituent.
Examples of the aryl group include the same groups as the aryl
groups described for the above-described R.sup.1.
[0079] Examples of the halogen atom represented by R.sup.4 in the
above formula (6) include a fluorine atom, a chlorine atom, a
bromine atom, and an iodine atom. In terms of conversion efficiency
when the fullerene derivative is used in the organic photoelectric
conversion device, a fluorine atom is preferred.
[0080] In the above formula (6), h represents an integer of 0 to 5,
provided that when h is 0, f is an integer of 1 to 4. In terms of
conversion efficiency when the fullerene derivative is used in the
organic photoelectric conversion device, h is preferably 0 or
1.
[0081] Among the fullerene derivatives having a group represented
by the above formula (6), fullerene derivatives represented by the
following formula (13) are preferred in terms of solubility in
organic solvents.
##STR00019##
wherein j represents an integer of 1 to 4; and R.sup.4, c, d, and e
represent the same meanings as described above.
[0082] In the above formula (13), c is preferably 2, d is
preferably 2, e is preferably 0, and j is preferably 1, in terms of
conversion efficiency when the fullerene derivative is used in the
organic photoelectric conversion device. R.sup.4 is preferably a
halogen atom or an alkyl group.
[0083] Among the fullerene derivatives represented by the above
formula (13), fullerene derivatives represented by the following
formula (14) are preferred in terms of conversion efficiency when
the fullerene derivative is used in the organic photoelectric
conversion device.
##STR00020##
wherein c, d, and e represent the same meanings as described above;
and R.sup.16 represents a fluorine atom or an alkyl group having 1
to 4 carbon atoms.
EXAMPLES
[0084] Examples will be illustrated below for describing the
present invention in more detail, but the present invention is not
limited to these.
[0085] For reagents and solvents used in synthesis, commercial
products were used as they were, or products, which were distilled
and purified in the presence of a desiccant, were used. For
C.sub.60 fullerene, one manufactured by Frontier Carbon Corporation
was used. NMR spectra were measured using MH500 manufactured by
JEOL, and tetramethylsilane (TMS) was used as the internal
standard. Infrared absorption spectra were measured using FR-IR
8000 manufactured by SHIMADZU CORPORATION. MALDI-TOF MS spectra
were measured using AutoFLEX-T2 manufactured by BRUKER.
Example 1
Synthesis of Fullerene Derivative A
Synthesis of Benzyl(2-(2-hydroxyethoxy)ethylamino)acetate
##STR00021##
[0086] (First Step) Bromoacetic acid (20.8 g, 150 mmol), benzyl
alcohol (16.2 g, 150 mmol), para-toluenesulfonic acid (258 mg, 1.5
mmol), and benzene (300 mL) were added to a two-necked flask
equipped with a Dean-Stark trap and were subjected to dehydration
condensation at 120.degree. C. for 24 hours. The solvent was
evaporated under reduced pressure by an evaporator, and then, the
residue was purified by silica gel flash column chromatography
(hexane/ethyl acetate=10/1, 5/1) to quantitatively obtain
bromoacetic acid benzyl ester (34.3 g, 150 mmol) as a yellow oily
material. R.sub.f 0.71 (hexane/ethyl acetate=4/1); .sup.1H NMR (500
MHz, ppm, CDCl.sub.3, J=Hz) .delta. 3.81 (s, 2H), 5.14 (s, 2H),
7.31 (s, 5H); .sup.13C NMR (125 MHz, ppm, CDCl.sub.3) .delta.
25.74, 67.79, 128.27, 128.48, 128.54, 134.88, 166.91; IR (neat,
cm.sup.-1) 2959, 1751, 1458, 1412, 1377, 1167, 972, 750, 698.
(Second Step) In an argon atmosphere, triethylamine (17 mL, 120
mmol) was added to a dichloromethane (90 mL) solution of
bromoacetic acid benzyl ester (13.7 g, 60 mmol) at 0.degree. C.,
and the obtained liquid mixture was stirred at the same temperature
for 20 minutes. Then, a dichloromethane (40 mL) solution of
2-(2-aminoethoxy)ethanol (12 mL, 120 mmol) was added, and the
mixture was stirred at room temperature for 4 hours. Then, the
organic layer was washed with water (3 times), and then dried with
anhydrous magnesium sulfate. The solvent was evaporated under
reduced pressure by the evaporator, and then, the residue was
purified by silica gel flash column chromatography (developing
solvent=ethyl acetate/methanol=1/0, 10/1, 5/1) to obtain glycine
ester 2 (12.2 g, 48.0 mmol) as a colorless oily material, with a
yield of 80%. R.sub.f 0.48 (ethyl acetate/methanol=2/1); .sup.1H
NMR (500 MHz, ppm, CDCl.sub.3, J=Hz) .delta. 2.83 (t, 2H, J=5.1
Hz), 3.50 (s, 2H), 3.52 (t, 2H, J=4.6 Hz), 3.58 (t, 2H, J=5.0 Hz),
3.65 (t, 2H, J=4.6 Hz), 5.11 (s, 2H), 7.28-7.30 (m, 5H); .sup.13C
NMR (125 MHz, ppm, CDCl.sub.3) .delta. 48.46, 50.25, 61.29, 66.38,
69.80, 72.23, 126.63, 128.12, 128.37, 135.30, 171.78; IR (neat,
cm.sup.-1) 3412, 2880, 1719, 1638, 1560, 1508, 1458, 1067, 669.
Synthesis of (2-(2-methoxyethoxy)ethylamino)acetic acid (1)
##STR00022##
[0087] (First Step) In an argon atmosphere, triethylamine (4.3 mL,
31 mmol) was added to a dichloromethane (50 mL) solution of benzyl
2-(2-(2-hydroxyethoxy)ethylamino)acetate (2) (6.58 g, 26 mmol) at
0.degree. C., and then, 4-(N,N-dimethylamino)pyridine (DMAP) (32
mg, 0.26 mmol) was added. The obtained liquid mixture was stirred
for 20 minutes, and then, a dichloromethane (10 mL) solution of
di-tert-butyl dicarbonate (6.77 g, 31 mmol) was dropped into the
liquid mixture. The reaction liquid mixture was stirred at room
temperature for 4 hours, and then poured into an Erlenmeyer flask
containing water to stop reaction. Diethyl ether extraction (3
times) was performed. The organic layer was dried, then
concentrated under reduced pressure, and then, purified by silica
gel flash column chromatography (developing solvent: hexane/ethyl
acetate=3/1, 2.5/1, 2/1) to obtain
benzyl{tert-butoxycarbonyl-[2-(2-hydroxy-ethoxy)ethyl]amino}acetate
(5.83 g, 16.5 mmol) as a colorless oily material, with a yield of
63%. R.sub.f 0.58 (ethyl acetate/methanol=20/1); .sup.1H NMR (500
MHz, ppm, CDCl.sub.3, J=Hz) .delta. 1.34 (d, 9H, J=54.5 Hz), 2.19
(brs, 1H), 3.38-3.45 (m, 4H), 3.50-3.60 (m, 4H), 3.99 (d, 2H,
J=41.3 Hz), 5.09 (d, 2H, J=4.1 Hz), 7.25-7.30 (m, 5H); .sup.13C NMR
(125 MHz, ppm, CDCl.sub.3) .delta. 27.82, 28.05, 47.90, 48.20,
49.81, 50.39, 61.23, 66.42, 69.92, 72.12, 80.08, 127.93, 128.14,
135.25, 154.99, 155.19, 169.94, 170.07; IR (neat, cm.sup.-1) 3449,
2934, 2872, 1751, 1701, 1458, 1400, 1367, 1252, 1143;
C.sub.18H.sub.27NO.sub.6 Anal.: Calcd.: C, 61.17; H, 7.70; N, 3.96.
Measured: C, 60.01; H, 7.75; N, 4.13. (Second Step) In an argon gas
atmosphere, a tetrahydrofuran (THF) (20 mL) solution of
benzyl{tert-butoxycarbonyl-[2-(2-hydroxy-ethoxy)ethyl]amino}acetate
(5.83 g, 16.5 mmol) was dropped into a THF (10 mL) solution of
sodium hydride (1.2 g, 24.8 mmol, 50% in mineral oil) at 0.degree.
C., and the mixture was stirred at the same temperature for 20
minutes. Then, iodomethane (1.6 mL, 24.8 mmol) was added at
0.degree. C. The reaction liquid mixture was stirred at room
temperature for 20 hours, and then, water was added, while the
reaction liquid mixture was cooled in an ice bath, to stop
reaction. Ether extraction (3 times) was performed. The organic
layer was dried, then concentrated under reduced pressure, and
purified by silica gel flash column chromatography (developing
solvent: hexane/ethyl acetate=5/1, 3/1) to obtain
benzyl{tert-butoxycarbonyl-[2-(2-methoxy-ethoxy)ethyl]amino}acetate
(3.02 g, 8.21 mmol) as a colorless oily material, with a yield of
50%. R.sub.f 0.54 (hexane/ethyl acetate=1/1); .sup.1H NMR (500 MHz,
ppm, CDCl.sub.3, J=Hz) .delta. 1.34 (d, 9H, J=51.8 Hz), 3.28 (d,
3H, J=2.7 Hz), 3.37-3.46 (m, 6H), 3.52 (dt, 2H, J=5.4 Hz, 16.5 Hz),
4.02 (d, 2H, J=34.8 Hz), 5.09 (d, 2H, J=4.5 Hz), 7.24-7.30 (m, 5H);
.sup.13C NMR (125 MHz, ppm, CDCl.sub.3) .delta. 24.93, 25.16,
44.68, 45.00, 46.70, 47.40, 55.78, 63.30, 67.22, 68.60, 76.95,
124.98, 125.14, 125.36, 132.49, 151.99, 152.31, 166.84, 166.96; IR
(neat, cm.sup.-1) 2880, 1751, 1701, 1560, 1458, 1400, 1366, 1117,
698, 617; C.sub.19H.sub.29NO.sub.6 Anal.: Calcd.: C, 62.11; H,
7.96; N, 3.81. Measured: C, 62.15; H, 8.16; N, 3.83. (Third Step)
In an argon atmosphere, trifluoroacetic acid (TFA) (9.0 mL) was
added to a dichloromethane (17 mL) solution of
benzyl{tert-butoxycarbonyl-[2-(2-methoxy-ethoxy)ethyl]amino}acetate
(3.02 g, 8.21 mmol), and the mixture was stirred at room
temperature for 7 hours. Then, 10% sodium carbonate aqueous
solution was added to adjust to pH 10, and dichloromethane
extraction was performed. The organic layer was dried with
anhydrous magnesium sulfate and concentrated under reduced pressure
to quantitatively obtain
benzyl[2-(2-methoxy-ethoxy)ethylamino]acetate (2.18 g, 8.19 mmol)
as a yellow oily material. R.sub.f 0.32 (ethyl
acetate/methanol=20/1); .sup.1H NMR (500 MHz, ppm, CDCl.sub.3,
J=Hz) .delta. 1.99 (brs, 1H), 2.83 (t, 2H, J=5.3 Hz), 3.38 (s, 3H),
3.50 (s, 2H), 3.54 (t, 2H, J=4.6 Hz), 3.60-3.62 (m, 4H), 5.17 (s,
2H), 7.32-7.38 (m, 5H); .sup.13C NMR (125 MHz, ppm, CDCl.sub.3)
.delta. 48.46, 50.66, 58.76, 66.20, 70.00, 70.44, 71.64, 128.09,
128.33, 135.44, 171.84; IR (neat, cm.sup.-1) 3350, 2876, 1736,
1560, 1458, 1117, 1030, 698, 619; C.sub.14H.sub.21NO.sub.4 Anal.:
Calcd.: C, 62.90; H, 7.92; N, 5.24. Measured: C, 62.28; H, 8.20; N,
5.05. (Fourth Step) Activated carbon (219 mg) supporting 10 wt %
palladium was added to a methanol (27 mL) solution of
benzyl[2-(2-methoxy-ethoxy)ethylamino]acetate (2.19 g, 8.19 mmol)
at room temperature. Hydrogen gas purging was performed, and then,
in a hydrogen atmosphere, the mixture was stirred at room
temperature for 7 hours. Pd/C were removed by a glass filter in
which a celite pad was laid, and the celite layer was washed with
methanol. The filtrate was concentrated under reduced pressure to
obtain [2-(2-methoxyethoxy)ethylamino]acetic acid (1) (1.38 g, 7.78
mmol) as a yellow oily material, with a yield of 95%. .sup.1H NMR
(500 MHz, ppm, MeOD, J=Hz) .delta. 3.21 (t, 2H, J=5.1 Hz), 3.38 (s,
3H), 3.51 (s, 2H), 3.57 (t, 2H, J=4.4 Hz), 3.65 (t, 2H, J=4.6 Hz),
3.73 (t, 2H, J=5.1 Hz); .sup.13C NMR (125 MHz, ppm, MeOD) .delta.
48.13, 50.49, 59.16, 67.08, 71.05, 72.85, 171.10; IR (neat,
cm.sup.-1) 3414, 2827, 1751, 1630, 1369, 1111, 1028, 851, 799;
C.sub.7H.sub.15NO.sub.4 Anal.: Calcd.: C, 47.45; H, 8.53; N, 7.90.
Measured: C, 46.20; H, 8.49; N, 7.43.
Synthesis of N-methoxyethoxyethyl-2-(1-naphthyl)fulleropyrrolidine
(Fullerene Derivative A)
##STR00023##
[0089] A fullerene derivative A was synthesized by the 1,3-dipolar
cycloaddition reaction of fullerene and iminium cations produced by
the decarboxylation of imine produced from a glycine derivative 1
and 1-naphthoaldehyde (Prato reaction).
[0090] In an argon atmosphere generated in a system, C.sub.60 (500
mg, 0.69 mmol), the glycine derivative 1 (185 mg, 1.04 mmol),
1-naphthylaldehyde (217 mg, 1.39 mmol), and chlorobenzene (100 mL)
were mixed in a three-neck flask equipped with a Dimroth condenser,
and heated to reflux at 150.degree. C. for 3 hours. The mixture was
allowed to cool to room temperature, and the solvent was evaporated
under reduced pressure by a rotary evaporator. The obtained solids
were separated and purified by silica gel flash column
chromatography (developing solvent: carbon disulfide/ethyl
acetate=1/0 to 20/1) to obtain the target fullerene derivative A
(356 mg, 0.36 mmol, yield: 52%) as a brown powder. The obtained
powder was washed with methanol five times, and then dried under
reduced pressure.
[0091] .sup.1H NMR (500 MHz, ppm, CDCl.sub.3, J=Hz) .delta.
2.89-2.94 (1H, m), 3.43 (3H, s), 3.43-3.50 (1H, m), 3.62-3.65 (2H,
m), 3.76-3.78 (2H, m), 3.96-4.00 (1H, m), 4.05-4.10 (1H, m), 4.49
(1H, d, J=10.0 Hz), 5.31 (1H, d, J=10.0 Hz), 6.16 (1H, s),
7.44-7.45 (2H, m), 7.62 (1H, t, J=8.0 Hz), 7.83 (1H, d, J=9.0 Hz),
7.87 (1H, d, J=8.0 Hz), 8.39 (1H, d, J=6.0 Hz), 8.52 (1H, d, J=8.0
Hz); .sup.13C NMR (125 MHz, ppm, CDCl.sub.3) .delta. 51.98, 59.19,
67.71, 69.50, 70.51, 72.04, 76.29, 123.91, 125.52, 125.81, 126.11,
128.07, 128.63, 129.16, 132.65, 133.19, 133.99, 135.47, 135.87,
136.13, 136.66, 139.26, 139.49, 140.14, 140.34, 141.56, 141.64,
141.77, 141.97, 142.04, 142.11, 142.24, 142.27, 142.30, 142.56,
142.66, 142.93, 143.10, 144.23, 144.39, 144.57, 144.64, 145.09,
145.20, 145.25, 145.29, 145.44, 145.55, 145.68, 145.74, 145.92,
146.07, 146.20, 146.73, 147.04, 147.25, 147.31, 153.70, 154.17,
154.26, 156.81; IR (KBr, cm.sup.-1) 2808, 1508, 1456, 1425, 1178,
1107, 773, 527; MALDI-TOF-MS (matrix: SA) Measured 991.203 (exact
mass calculated for C.sub.77H.sub.21NO.sub.2: 991.173).
Example 2
Synthesis of
N-methoxyethoxyethyl-2-(perfluorophenyl)fulleropyrrolidine
(Fullerene Derivative B)
##STR00024##
[0093] Fullerene C.sub.60 (250 mg, 0.35 mmol), the glycine
derivative 1 (92 mg, 0.52 mmol), and pentafluorobenzaldehyde (136
mg, 0.69 mmol) in 50 mL of chlorobenzene were heated to reflux for
2 hours, and purification was performed by operation similar to
that of Example 1 to obtain 179 mg (0.17 mmol, yield 50%) of a
fullerene derivative B.
[0094] .sup.1H NMR (500 MHz, ppm, CDCl.sub.3, J=Hz) .delta.
3.08-3.14 (1H, m), 3.37-3.42 (1H, m), 3.45 (3H, s), 3.65-3.68 (2H,
m), 3.80-3.82 (2H, m), 3.95-3.99 (1H, m), 4.12-4.17 (1H, m), 4.35
(1H, dd, J=10.0 Hz, 3.0 Hz), 5.18 (1H, d, J=19.0 Hz), 5.79 (1H, s);
.sup.13C NMR (125 MHz, ppm, CDCl.sub.3) .delta. 51.85, 58.70,
66.68, 69.06, 69.57, 70.59, 71.90, 72.86, 72.89, 74.57, 125.13,
128.03, 128.77, 135.26, 135.63, 136.37, 137.82, 139.33, 139.97,
140.00, 140.04, 141.37, 141.41, 141.44, 141.67, 141.69, 141.83,
141.90, 141.99, 142.38, 142.47, 142.81, 142.87, 144.05, 144.17,
144.24, 144.49, 144.96, 145.02, 145.10, 145.13, 145.18, 145.28,
145.32, 145.41, 145.73, 145.83, 145.86, 145.94, 146.06, 146.09,
147.06, 147.08, 150.76, 152.02, 153.14, 155.40; .sup.19F NMR (470
MHz, ppm, CDCl.sub.3, J=Hz) .delta. 9.24 (1F, d, J=23.0 Hz), 21.68
(2F, d, J=23.0 Hz), 28.48 (2F, d, J=17.0 Hz); IR (Neat, cm.sup.-3)
2873, 1523, 1501, 1107, 997, 754, 527; MALDI-TOF-MS (neat) Measured
1031.234 (exact mass calculated for C73H14F5NO2: 1031.094).
Example 3
Synthesis of N-methoxyethoxyethyl-2-(4-fluorophenyl)
fulleropyrrolidine (Fullerene Derivative C)
##STR00025##
[0096] Fullerene C.sub.60 (250 mg, 0.35 mmol), the glycine
derivative 1 (92 mg, 0.52 mmol), and 4-fluorobenzaldehyde (86 mg,
0.69 mmol) in 50 mL of chlorobenzene were heated to reflux for 2
hours. Purification was performed by operation similar to that of
Example 1 to obtain 192 mg (0.20 mmol, yield: 58%) of a fullerene
derivative C.
[0097] .sup.1H NMR (500 MHz, ppm, CDCl.sub.3, J=Hz) .delta.
2.82-2.85 (1H, m), 3.37 (3H, s), 3.59-3.61 (2H, m), 3.71-3.74 (2H,
m), 3.92-3.94 (1H, m), 3.97-4.00 (1H, m), 4.27 (1H, d, J=19.0 Hz),
5.19 (1H, s), 5.20 (1H, d, J=19.0 Hz), 7.04 (2H, t, J=17.0 Hz),
7.75 (2H, br); .sup.13C NMR (125 MHz, ppm, CDCl.sub.3) .delta.
52.01, 59.19, 67.63, 69.11, 70.41, 70.59, 72.07, 76.21, 81.62,
115.59, 115.74, 131.03, 131.09, 132.98, 135.63, 135.90, 136.45,
136.91, 139.47, 139.90, 140.14, 140.19, 141.53, 141.68, 141.82,
141.87, 141.98, 142.02, 142.05, 142.10, 142.13, 142.17, 142.27,
142.55, 142.57, 142.69, 143.00, 143.17, 144.36, 144.42, 144.59,
144.72, 145.15, 145.21, 145.26, 145.33, 145.52, 145.72, 145.94,
145.95, 146.04, 146.11, 146.14, 146.17, 146.21, 146.28, 146.30,
146.46, 146.61, 147.32, 153.16, 153.29, 154.13, 156.47, 161.72;
.sup.19F NMR (470 MHz, ppm, CDCl.sub.3) .delta. 49.55 (1F, s); IR
(neat, cm.sup.-1) 2880, 1508, 1225, 1109, 754, 527; MALDI-TOF-MS
(matrix: SA) Measured 958.476 (exact mass calculated for
C73H18FNO2: 959.132).
Example 4
Synthesis of
N-methoxyethoxyethyl-2-(4-methylphenyl)fulleropyrrolidine
(Fullerene Derivative D)
##STR00026##
[0099] Fullerene C.sub.60 (250 mg, 0.35 mmol), the glycine
derivative 1 (92 mg, 0.52 mmol), and 4-fluorobenzaldehyde (83 mg,
0.69 mmol) in 50 mL of chlorobenzene were heated to reflux for 2
hours. Purification was performed by operation similar to that of
Example 1 to obtain 133 mg (0.14 mmol, yield: 40%) of a fullerene
derivative D.
Synthesis Example 1
Synthesis of N-methoxyethoxyethyl-2-phenyl-fulleropyrrolidine
(Fullerene Derivative E)
##STR00027##
[0101] Fullerene C.sub.60 (250 mg, 0.35 mmol), the glycine
derivative 1 (92 mg, 0.52 mmol), and 4-fluorobenzaldehyde (83 mg,
0.69 mmol) in 50 mL of chlorobenzene were heated to reflux for 2
hours. Purification was performed by operation similar to that of
Example 1 to obtain 133 mg (0.14 mmol, yield: 40%) of a fullerene
derivative E.
Example 5
Synthesis of Fullerene Derivative F
##STR00028##
[0103] Fullerene C.sub.60 (250 mg, 0.35 mmol), the glycine
derivative 1 (92 mg, 0.52 mmol), and 4-trifluoromethylbenzaldehyde
(121 mg, 0.69 mmol) in 50 mL of chlorobenzene were heated to reflux
for 2 hours. Purification was performed by operation similar to
that of Example 1 to obtain 170 mg (0.17 mmol, yield: 49%) of a
fullerene derivative F.
Example 6
Synthesis of
N-methoxyethoxyethyl-2-(2-phenylethyl)fulleropyrrolidine (Fullerene
Derivative G)
##STR00029##
[0105] Fullerene C.sub.60 (250 mg, 0.35 mmol), the glycine
derivative 1 (92 mg, 0.52 mmol), and 3-phenylpropionaldehyde (93
mg, 0.69 mmol) in 50 mL of chlorobenzene were heated to reflux for
2 hours. Purification was performed by operation similar to that of
Example 1 to obtain 164 mg (0.17 mmol, yield: 48%) of a fullerene
derivative G.
Example 7
Synthesis of N-methoxyethoxyethyl-2-(2-naphthyl) fulleropyrrolidine
(Fullerene Derivative H)
##STR00030##
[0107] Fullerene O.sub.60 (500 mg, 0.69 mmol), the glycine
derivative 1 (185 mg, 1.04 mmol), and 2-naphthoaldehyde (217 mg,
1.39 mmol) in 100 mL of chlorobenzene were heated to reflux for 3
hours. Purification was performed by operation similar to that of
Example 1 to obtain 262 mg (0.26 mmol, yield: 38%) of a fullerene
derivative H.
[0108] .sup.1H NMR (500 MHz, ppm, CDCl.sub.3, J=Hz) .delta.
2.90-2.95 (1H, m), 3.44 (3H, s), 3.65-3.67 (2H, m), 3.76-3.80 (2H,
m), 3.97-4.02 (1H, m), 4.05-4.10 (1H, m), 4.36 (1H, d, J=19.0 Hz),
5.26 (1H, d, J=20.0 Hz), 5.34 (1H, s), 7.47-7.49 (3H, m), 7.83-7.90
(4H, m); .sup.13C NMR (125 MHz, ppm, CDCl.sub.3) .delta. 52.12,
59.17, 67.73, 69.38, 70.49, 72.06, 76.39, 126.18, 126.25, 127.79,
128.09, 128.50, 133.47, 134.81, 135.66, 136.56, 136.92, 139.48,
139.87, 140.14, 141.47, 141.67, 141.75, 141.86, 141.92, 142.01,
142.64, 142.11, 142.14, 142.28, 142.48, 142.52, 142.65, 142.97,
143.11, 144.36, 144.39, 144.54, 144.70, 145.12, 145.17, 145.23,
145.32, 145.51, 145.55, 145.58, 145.73, 145.90, 146.10, 146.14,
146.19, 146.29, 146.48, 146.78, 147.27, 153.32, 153.57, 154.38,
156.51; IR (neat, cm.sup.-1) 2922, 1215, 1184, 1109, 752, 669, 527;
MALDI-TOF-MS (matrix: SA) Measured 990.629 (exact mass calculated
for C.sub.77H.sub.21NO.sub.2: 991.173).
Evaluation Examples 1 to 8
Evaluation of Solubility in Xylene
[0109] A xylene solvent was added to a fullerene derivative shown
in Table 1 at a concentration of 1 wt %, and the mixture was
stirred by a magnetic stirrer for 10 minutes. The subsequent
solubility in xylene solvent was visually observed. The results are
shown in Table 1.
TABLE-US-00001 TABLE 1 Fullerene Solubility of a derivative 1 wt %
xylene solution Evaluation Example 1 A Dissolved Evaluation Example
2 B Dissolved Evaluation Example 3 C Dissolved Evaluation Example 4
D Dissolved Evaluation Example 5 E Dissolved Evaluation Example 6 F
Dissolved Evaluation Example 7 G Dissolved Evaluation Example 8
[60] PCBM Insoluble matter is present
(Fabrication and Evaluation of Organic Thin Film Solar Cell)
[0110] Regioregular poly(3-hexylthiophene) (manufactured by
Aldrich, lot number: 15409BE, Mw=41000, Mn=22000) as an electron
donor was dissolved in o-dichlorobenzene at a concentration of 1%
(wt %). Then, a fullerene derivative shown in Table 2 was mixed in
the solution as an electron acceptor having a weight equal to the
weight of the electron donor. Then, the mixture was filtered by a
1.0 .mu.m Teflon (registered trademark) filter to make a coating
solution.
[0111] A glass substrate on which an ITO film with a thickness of
150 nm was provided by sputtering was subjected to ozone-UV
treatment for surface treatment. Next, the substrate was coated
with the above coating solution by spin coating to obtain the
activity layer (film thickness: about 100 nm) of an organic thin
film solar cell. Then, the substrate was baked under conditions of
90.degree. C. in a vacuum for 60 minutes. Then, lithium fluoride
with a thickness of 4 nm was vapor-deposited by a vacuum deposition
machine, and then, A1 with a thickness of 100 nm was
vapor-deposited. The degree of vacuum during vapor deposition was 1
to 9.times.10.sup.-3 Pa for all. The shape of the obtained organic
thin film solar cell was a 2 mm.times.2 mm square. The
photoelectric conversion efficiency of the obtained organic thin
film solar cell was obtained by emitting constant light using a
solar simulator (manufactured by Bunkoukeiki Co., LTD., trade name:
OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW/cm.sup.2), and
measuring generated current and voltage. The results are shown in
Table 2.
TABLE-US-00002 TABLE 2 Fullerene Photoelectric conversion
derivative efficiency (%) Example 8 A 2.6 Example 9 C 2.7 Example
10 D 2.7 Example 11 E 2.6 Example 12 H 2.6 Comparative Example 1
[60] PCBM 2.3 [60] PCBM (Phenyl C61-butyric acid methyl ester,
manufactured by Frontier Carbon Corporation, trade name: E100)
Example 13
Synthesis of N-methoxyethoxyethyl-2-(4-biphenyl) fulleropyrrolidine
(Fullerene Derivative I)
##STR00031##
[0113] Fullerene C.sub.60 (250 mg, 0.35 mmol), the glycine
derivative 1 (92 mg, 0.52 mmol), and biphenyl-4-carboxaldehyde (126
mg, 0.69 mmol) were placed in a two-neck flask (100 mL) equipped
with a Dimroth condenser, and chlorobenzene (50 mL) was added. The
mixture was heated to reflux for 3 hours. The mixture was allowed
to cool to room temperature, and then, the solvent was removed by
the rotary evaporator. Then, the residue was purified using silica
gel flash column chromatography (developing solvent: carbon
disulfide/ethyl acetate=1/0 to 20/1) to obtain 150 mg (0.15 mmol,
42%) of a fullerene derivative I (brown powder). This powder was
washed with methanol five times, and then dried under reduced
pressure.
[0114] .sup.1H NMR (400 MHz, ppm, CDCl.sub.3, J=Hz) .delta.
2.84-2.90 (1H, m), 3.36-3.48 (2H, m), 3.40 (3H, s), 3.57-3.66 (2H,
m), 3.71-3.80 (2H, m), 3.93-3.98 (1H, m), 4.00-4.06 (1H, m), 4.29
(1H, d, J=9.5 Hz), 5.17 (1H, s), 5.22 (1H, d, J=9.9 Hz), 7.26 (1H,
dt, J.sub.1=1.1 Hz, J.sub.2=7.7 Hz), 7.35 (2H, dd, J.sub.1=8.4 Hz,
J.sub.2=7.0 Hz), 7.52 (2H, dd, J.sub.1=1.1 Hz, J.sub.2=8.2 Hz),
7.58 (2H, d, J=8.4 Hz), 7.82 (d, 2H, J=7.82 Hz); .sup.13C NMR (100
MHz, ppm, CDCl.sub.3) .delta. 41.83, 48.49, 57.29, 58.66, 60.22,
61.67, 65.70, 71.72, 116.45, 116.51, 116.82, 116.92, 117.73,
118.29, 118.49, 119.39, 125.12, 125.58, 126.01, 126.38, 129.02,
129.41, 129.61, 129.61, 129.86, 130.69, 130.99, 131.12, 131.35,
131.42, 131.47, 131.52, 131.60, 131.73, 132.01, 132.44, 132.59,
133.80, 133.84, 134.07, 134.15, 134.56, 134.63, 134.68, 134.74,
134.81, 134.94, 135.01, 135.20, 135.35, 135.52, 135.55, 135.60,
135.63, 135.70, 135.70, 135.75, 135.89, 136.21, 136.70, 142.74,
142.90, 143.63, 145.88; IR (KBr, cm.sup.-1) 3435, 2864, 2803, 1485,
1462, 1427, 1337, 1304, 1179, 1107, 1007, 843, 762, 694, 527;
MALDI-TOF-MS (matrix: SA) Measured 1016.3050 (exact mass calculated
for C.sub.79H.sub.23NO.sub.2.sup.+: 1017.1729).
Example 14
Synthesis of
N-methoxyethoxyethyl-2-(4-methoxyphenyl)fulleropyrrolidine
(Fullerene Derivative J)
##STR00032##
[0116] 100 mL of chlorobenzene was added to fullerene C.sub.60 (500
mg, 0.69 mmol), the glycine derivative 1 (185 mg, 1.04 mmol), and
4-methoxybenzaldehyde (189 mg, 1.39 mmol), and the mixture was
heated to reflux for 2 hours. The solvent was evaporated under
reduced pressure, and then, the residue was purified using silica
gel flash column chromatography (developing solvent: carbon
disulfide/toluene/ethyl acetate=1/0/0 to 0/40/1) to obtain 312 mg
(0.321 mmol, 42%) of a fullerene derivative J. This powder was
washed with methanol five times, and then dried under reduced
pressure.
[0117] .sup.1H NMR (400 MHz, ppm, CDCl.sub.3, J=Hz) .delta.
2.78-2.84 (1H, m), 3.39 (3H, s), 3.35-3.45 (1H, m), 3.56-3.63 (2H,
m), 3.69-3.79 (2H, m), 3.75 (3H, s), 3.89-3.94 (1H, m), 3.96-4.02
(1H, m), 4.24 (1H, d, J=9.8 Hz), 5.06 (1H, s), 5.17 (1H, d, J=9.7
Hz), 6.86 (2H, d, J=8.3 Hz), 7.64 (2H, d, J=6.9 Hz); .sup.13C NMR
(100 MHz, ppm, CDCl.sub.3) .delta. 51.99, 54.62, 58.74, 67.49,
68.77, 70.47, 70.52, 71.95, 76.14, 81.76, 113.84, 128.01, 128.62,
130.23, 135.41, 135.53, 136.28, 136.53, 139.25, 139.66, 139.84,
139.90, 141.24, 141.37, 141.52, 141.63, 141.68, 141.80, 141.83,
141.86, 141.99, 142.26, 142.29, 142.37, 142.70, 142.85, 144.07,
144.35, 144.41, 144.81, 144.89, 144.89, 144.99, 145.05, 145.19,
145.27, 145.47, 145.60, 145.76, 145.80, 145.84, 145.94, 145.99,
146.07, 146.21, 146.50, 146.96, 153.30, 153.35, 153.94, 156.28,
159.27; IR (KBr, cm.sup.-1) 3460, 3893, 2866, 2828, 1609, 1508,
1456, 1429, 1302, 1246, 1180, 1171, 1107, 1034, 831, 573, 527;
MALDI-TOF-MS (matrix: SA) Measured 971.1522 (exact mass calculated
for C.sub.74H.sub.21NO.sub.3.sup.+: 971.1521).
Example 15
Synthesis of
N-methoxyethoxyethyl-2-(4-chlorophenyl)fulleropyrrolidine
(Fullerene Derivative K)
##STR00033##
[0119] Fullerene C.sub.60 (500 mg, 0.69 mmol), the glycine
derivative 1 (184 mg, 1.04 mmol), and 4-chlorobenzaldehyde (196 mg,
1.39 mmol) were placed in a two-neck flask (200 mL) equipped with a
Dimroth condenser, and chlorobenzene (100 mL) was added. The
mixture was heated to reflux for 2 hours. The mixture was allowed
to cool to room temperature, and then, the solvent was removed by
the rotary evaporator. Then, the residue was purified using silica
gel flash column chromatography (developing solvent: carbon
disulfide/ethyl acetate=1/0 to 20/1) to obtain 254 mg (0.26 mmol,
38%) of a fullerene derivative K (brown powder). This powder was
washed with methanol five times, and then dried under reduced
pressure.
[0120] .sup.1H NMR (500 MHz, ppm, CDCl.sub.3, J=Hz) .delta.
2.85-2.90 (1H, m), 3.37-3.47 (1H, m), 3.42 (3H, s), 3.62-3.65 (2H,
m), 3.71-3.80 (2H, m), 3.94-3.98 (1H, m), 4.01-4.05 (1H, m), 4.29
(1H, d, J=9.6 Hz), 5.14 (1H, s), 5.21 (1H, d, J=9.6 Hz), 7.37 (2H,
d, J=8.8 Hz), 7.75 (2H, d, J=4.6 Hz); .sup.13C NMR (100 MHz, ppm,
CDCl.sub.3) .delta. 52.02, 58.98, 67.51, 68.94, 70.34, 70.53,
71.98, 75.90, 81.52, 128.83, 130.58, 134.26, 135.48, 135.63,
135.79, 136.30, 136.83, 139.43, 139.81, 140.04, 140.07, 141.42,
141.55, 141.70, 141.83, 141.88, 141.93, 141.93, 141.98, 142.01,
142.11, 142.42, 142.55, 142.87, 142.87, 143.01, 144.20, 144.26,
144.45, 144.56, 145.01, 145.05, 145.05, 145.10, 145.14, 145.19,
145.29, 145.33, 145.40, 145.56, 145.81, 145.94, 145.99, 146.03,
146.06, 146.12, 146.16, 146.24, 146.39, 147.14, 152.71, 152.94,
153.84, 156.13; IR (KBr, cm.sup.-1) 2862, 2803, 1489, 1458, 1420,
1180, 1107, 1090, 1015, 839, 829, 598, 573, 527; MALDI-TOF-MS
(matrix: SA) Measured 975.1024 (exact mass calculated for
C.sub.73H.sub.18ClNO.sub.2.sup.+: 975.1026)
(Fabrication and Evaluation of Organic Thin Film Solar Cell)
[0121] Regioregular poly(3-hexylthiophene) (manufactured by
Aldrich, lot number: 01004AH, Mw=43000, Mn=22000) as an electron
donor was dissolved in o-dichlorobenzene at a concentration of 1%
(wt %). Then, a fullerene derivative shown in Table 3 was mixed in
the solution as an electron acceptor having a weight equal to the
weight of the electron donor. Then, the mixture was filtered by a
Teflon (registered trademark) filter having a pore diameter of 1.0
.mu.m to make a coating solution.
[0122] A glass substrate on which an ITO film with a thickness of
150 nm was provided by sputtering was subjected to ozone-UV
treatment for surface treatment. Next, the substrate was coated
with the above coating solution by spin coating to obtain the
activity layer (film thickness: about 100 nm) of an organic thin
film solar cell. Then, the substrate was baked under conditions of
90.degree. C. in a vacuum for 60 minutes. Then, lithium fluoride
with a thickness of 4 nm was vapor-deposited by the vacuum
deposition machine, and then, A1 with a thickness of 100 nm was
vapor-deposited. The degree of vacuum during vapor deposition was 1
to 9.times.10.sup.-3 Pa for all. The shape of the obtained organic
thin film solar cell was a 2 mm.times.2 mm square. The
photoelectric conversion efficiency of the obtained organic thin
film solar cell was obtained by emitting constant light using the
solar simulator (manufactured by Bunkoukeiki Co., LTD., trade name:
OTENTO-SUNII: AM1.5G filter, irradiance: 100 mW/cm.sup.2), and
measuring generated current and voltage. The results are shown in
Table 3.
TABLE-US-00003 TABLE 3 Fullerene Photoelectric conversion
derivative efficiency (%) Example 16 I 2.3 Example 17 J 2.2 Example
18 K 2.5 Comparative Example 2 [60] PCBM 2.0 [60] PCBM (Phenyl
C61-butyric acid methyl ester, manufactured by Frontier Carbon
Corporation, trade name: E100)
--Evaluation--
[0123] As is seen from Table 1, the fullerene derivatives A to G
had better solubility in xylene than [60]PCBM. Also, the organic
thin film solar cells formed using the fullerene derivatives A, C,
D, E, H, I, J, and K (Examples 8 to 12 and 16 to 18) exhibited high
photoelectric conversion efficiency.
INDUSTRIAL APPLICABILITY
[0124] The organic photoelectric conversion device of the present
invention has high conversion efficiency.
* * * * *